7,7-dicyano-6,10-dimethyl-8-phenylundeca-1,4,10-triene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 7,7-dicyano-6,10-dimethyl-8-phenylundeca-1,4,10-triene
• 英文别名: 2-[(3E)-hepta-3,6-dien-2-yl]-2-(3-methyl-1-phenylbut-3-enyl)propanedinitrile
• 化学式: C₂₁H₂₄N₂
• 分子量: 304.435
• InChiKey: VLKPHPCGHUYVOJ-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  苄烯丙二腈 、 甲基烯丙基三正丁基锡 、 (4E)-6-chlorohepta-1,4-diene 在 四(三苯基膦)钯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以65%的产率得到7,7-dicyano-6,10-dimethyl-8-phenylundeca-1,4,10-triene
  参考文献：
  名称：

  Control of the Regioselectivity in Catalytic Transformations Involving Amphiphilic Bis-allylpalladium Intermediates:  Mechanism and Synthetic Applications

  摘要：

  Various dialkyl-substituted allyl chloride derivatives (2d-i) undergo regioselective palladium-catalyzed coupling reactions with allylstannanes (1a,b) and benzylidenemalonitrile (4), providing functionalized 1,7-octadienes in good yield. The catalytic reaction proceeds through an unsymmetrical amphiphilic bis-allylpalladium intermediate. An:introductory electrophilic attack on the terminal position of the unsubstituted alkyl moiety is followed by a nucleophilic attack on the alkyl-substituted allyl ligand. A theoretical analysis was performed by applying density functional theory at the B3PW91/DZ+P level to study the substituent effects on the electrophilic attack. According to the theoretical results, the high regioselectivity can be ascribed to the electronic effects of the alkyl substituents: The terminal alkyl groups destabilize the eta (1),eta (3)-bis-allylpalladium intermediate of the reaction; in addition, the alkyl substitution increases the activation barrier for the electrophilic attack.

  DOI：

  10.1021/jo001374d